Selective carbonylation of olefinically unsaturated hydrocarbons using palladium-phosphine catalysts promoted with tin salts

ABSTRACT

A carbonylation process is provided for conversion of olefinically unsaturated hydrocarbons to a mixture of esters or acids with an increased ratio of normal:iso (i.e., straight: branched) ester or acid by reaction with carbon monoxide and a hydroxylic compound, said process being carried out in the presence of a palladium salt complexed with a phosphine ligand as a catalyst and tin cocatalysts or promoters. For example, the catalyst may be palladium dichloride bis(triphenylphosphine) and the tin cocatalyst or promoter present may be stannous chloride dihydrate.

United States Patent Butter Oct. 24, 1972 [54] SELECTIVE CARBONYLATIONOF [56] 7 References Cited OLEFINICALLY UNSATURATED HYDROCARBONS USINGPALLADIUM- UNITED STATES PATENTS PHOSPHINE CATALYSTS PROMOTED 2,876,2545/1959 Jenner et al. ..260/486 WITH TIN SALTS 3,437,676 4/1969 vonKutepow et al.....260/468 [72] Inventor: Stephen A. Butter, Boundbrook,2,963,499 12/1960 Aldridge et al ..260/4l0.9

Primary ExaminerLewis Gotts I73} Assignec: Mobil Oil CorporationAssistant Examiner-Diana G. Rivers Filed: g 17, 1970grtliiofieizgc-ggsgaglogioglayes, Andrew L. Gaboriault [2] I Appl. No:64,631

[57] ABSTRACT Related US. Application Data A carbonylation process isprovided for conversion of [63] commuatlon'm'pan of Sen 13,170olefinically unsaturated hydrocarbons to a mixture of 1970 abandonedesters or acids with an increased ratio of normalziso (i.e.,straightzbranched) ester or acid by reaction with [52] US. Cl..260/410.9 R, 260/408, 260/413, carbon monoxide and a hydroxyliccompound, Said 260M105 260/468 260/485 260/485 process being carried outin the presence of a palladi- 260/486 260/497 260/514 um salt complexedwith a phosphine ligand as a 260/533 260/544 A catalyst and tincocatalysts or promoters. For exam- [51] Int. Cl ..C07c 51/14 p16 thecatalyst may be palladium dichloride bis [58] Field of Search..260/410.9 R, g g g a -a aw -fsf 413, 410.5, 497 A, 2 0/5'3TA, 468 CB,.514 co, 514 CA moter present may be stannous chloride dihydrate.

13 Claims, No Drawings SELECTIVE CARBONYLATION OF OLEFINICALLYUNSATURATED HYDROCARBONS USING PALLADIUM- PHOSPHINE CATALYSTS PROMOTEDWITH TIN SALTS CROSS-REFERENCE TO RELATED APPLICATIONS This is acontinuation-in-part of application Ser. No. 13, 170, filed Feb. 20,1970 now abandoned.

BACKGROUND OF THE INVENTION 1. Field of the Invention This inventionrelates to a process of carbonylation of olefinically unsaturatedhydrocarbons to a mixture of esters or acids with an increased ratio ofnorrnalziso ester or acid, said process being carried out in thepresence of a palladium salt complexed with a phosphine ligand as acatalyst accompanied by a tin cocatalyst or promoter. More particularly,it relates to a process of carbonylation of olefinically unsaturatedhydrocarbons by reaction with carbon monoxide and a hydroxylic compoundin the presence of the above catalyst and cocatalyst or promoter toyield a mixture of esters or acids with an increased ratio of normalzisoester or acid.

11. Description of the Prior Art It is generally known that olefins,carbon monoxide and alcohols or water may be combined to form carboxylicacids or esters using catalysts based on group VIII metals which formcarbonyls.

Early carbonylation processes based on nickel catalysts utilizedvigorous reaction conditions and were accompanied by side reactions (W.Reepe, Liebigs Ann. Chem. 582, 1 [1953]). Octacarbonyldicobalt has alsobeen used to form carboxylic acids (R. Ercoll, Das 1092015, [1957]Montecatini).

There is also known a carbonylation process conducted under mildconditions with minimum byproduct formation which is based on palladiumcomplex salts as catalysts, examples of which include palladiumcatalysts containing phosphines, phosphites, ammonia, amines, nitriles,and unsaturated hydrocarbons as ligands(von Kutepow, et al, US. Pat. No.3,437,676), but with no tin or other cocatalysts or promoters present.

Also, the use of palladium dichloride in an alcoholic solution ofhydrogen chloride is known to convert olefins into esters (J. Tsuji, eta1, Tetrahedron Letters (1963) 1437).

In prior art known to the inventor, carbonylation of terminal olefinssuch as propylene results in mixtures of esters or acids such that theratio normalziso is usually about 0.33:1 to about 0.50:1.

SUMMARY OF THE INVENTION In accordance with this invention, there isprovided a carbonylation process using a palladium salt complexed with aphosphine ligand as a catalyst and a tin cocatalyst or promoter in whicholefinically unsaturated hydrocarbons are converted to a mixture ofesters or acids with an increased ratio of normal:iso ester or acid byreaction with carbon monoxide and a hydroxylic compound.

2 DESCRIPTION OF SPECIFIC EMBODIMENTS In prior art carbonylationprocesses employing catalysts such as 'palladium-phosphines without tincocatalysts or promoters, carbonylation of olefinically unsaturatedhydrocarbons such as propylene and isobutylene with carbon monoxide andan alcohol has resulted in mixtures of esters with a ratio 0.33:1 toabout 0.50: 1, normalziso ester.

In the present invention a carbonylation process utilizing apalladium-phosphine complex in combination with a tin cocatalyst orpromoter provides carbonylation, as in the case of propylene, to butyricacid esters (e.g., methyl isobutyrate and methyl-n-butyrate) with theratio of normal: iso ester generally better than 0.67:1 and in certainselected cases about 4:1.

Non-limiting examples of the olefinically unsaturated hydrocarbons whichmay be carbonylated according to the present invention are: ethylene,propylene, butenes, pentenes, hexenes, octenes, tetradecenes,octadecenes, cycloolefins, dienes such as butadiene, and trienes and, inmore general aspect, olefinically unsaturated hydrocarbons of from twoto 30 carbon atoms,

Hydroxylic compounds may be used, if desired, in practice of the presentinvention. If a hydroxylic compound is used in the carbonylation processof the present invention, it may be one of several possibilities withthe end product type being determined by the compound used. If alcoholis used, an ester is formed by the present process. If water is used,the product is an acid. Phenols may be used with the products beingesters. If no hydroxylic media is used, the products may be acylhalides.

Additionally, a solvent may be used, if desired, in the process of thepresent invention. However, the use of a suitable solvent is preferred.Non-limiting examples of solvents which may be used are: alcohols,ketones, esters, ethers, and aliphatic, aromatic and heterocyclichydrocarbons and other materials inert under the conditions of practiceof the present process.

If a solvent is used in the process of the present invention, animportant factor to be considered in the selectionof one to be suitablefor the particular carbonylation reaction in question is the boilingpoint increment between the solvent and the product. For example,p-xylene is a preferred solvent in the reaction which yields methylbutyrate esters since these esters boil 25-3 5C. below the solvent. Thisboiling point difference enables efficient separation of the solvent andproduct by simple distillation.

The reaction temperature during the process of the present invention maybe varied over a rather wide range and, for example, in the range offrom about 20C. to about 200C. Temperatures between ""C. and 100C. arepreferred.

The catalyst concentrations used in the present invention may be variedover a wide range. However, a concentration varying from as low as 0.001percent up to about 50 percent or more, is useful with the range of fromabout 0.1 to about 5 percent (based on the weight of the unsaturatedhydrocarbon reactant) being The process according to the presentinvention may be carried out under pressure sufficient to maintain aliquid phase with regard to the reactants. Depending upon the reactantsused (i.e., the olefinically unsaturated hydrocarbon and hydroxyliccompound), the pressure may vary between atmospheric to about 10,000psig. In general, pressures of from about 50 to about 1,500 psig. arepreferred and used.

In the practice of the carbonylation process of the present invention,the olefinically unsaturated hydrocarbon is reacted with carbon monoxideand a suitable hydroxylic compound, e.g., an alcohol, in the presence ofa catalyst of the formula L,,,PdX,,, wherein L is an organo-phosphineand X is an acid function, and a tin cocatalyst or promoter.

The tin cocatalyst or promoter to be present in the reaction may be ofseveral and varied organic or inorganic forms. Non-limiting examples oftin compounds which may be used include stannous chloride dihydrate,anhydrous stannous chloride, starmic chloride pentahydrate, andtriphenyltin chloride. The yield of normal (straight chain) product isincreased in the present invention as the tin moity is made moreelectronegative according to the series SnCl SnCl SnCl Theabove-mentioned acid function, X, of the catalyst of the process of thepresent invention may be any one of several acid functions with halideradicals andparticularly the chloride radical preferred. NOnlimitingexamples of acid functions which may be present in the catalyst of thepresent invention include chloride, bromide, iodide, sulfate, phosphate,acetate, nitrate, propionate, borate, and others.

Excess amounts of phosphine ligand over that amount required to form thecomplex and excess amounts :of tin cocatalyst or promoter are used incertain instances to stabilize the catalyst and, in some cases, withobtainment of increased yield of desired product. 3

The use of tin modified palladium catalysts, e.g., palladium-phosphinecatalysts with a tin cocatalyst or promoter, is valuable for directingthe course of carbon monoxide addition to olefinic double-bond and is,therefore, particularly useful for preparing straight chain acids andesters such as methyl-n-butyrate from propylene.

The reaction may be carried out in the presence, if desired, ofhydrohalic acids, particularly of hydrogen chloride. It is advantageousto have hydrohalic acids present because lower temperatures may then beused at a given catalyst concentration, or lower catalyst concentrationsat a given temperature. The acids are generally used in amounts of up to10 percent by weight with reference to the whole of the initialmaterials. They may be used in alcoholic or aqueous solution, butoptionally also in pure form.

The following examples illustrate the process of the present invention.The example results are summarized in the Table immediately followingthe examples.

EXAMPLE 1 A 300 cc. Hastelloy autoclave was charged with 0.50 g.palladium dichloride-bis(triphenylphosphine), 0.32 g. stannous chloridedihydrate, 2.3 g. hydrochloric acid and 80.0 g. of methanol. Liquidpropylene (6.6 g.) was pumped in and stirring was started. Thetemperature was raised to 91C. and the system pressured with carbonmonoxide to 1,000 psig. The reaction mixture was cooled after 3 hoursand the products were distilled and analyzed by gas chromatography. Theyield based on reacted propylene was practically quantitative andconsisted of 7.9 g. of methyl-n-butyrate and methyl-isobutyrate in aratio of 50 parts to 50 parts.

EXAMPLE 2 EXAMPLE 3 Following the procedure in Example 1, 20.0 g.propylene was added to 0.5 g. palladium dichloridebis(triphenylphosphine), 2. g. hydrochloric acid and 27.4 g. methanol in43.1 g. p-xylene. Carbon monoxide was added at 92C. to maintain a totalpressure of approximately 900 psi. After 3.3 hours, the productsconsisted of 42.5 of methyl butyrate esters in a ratio of 43 partsstraight-chain to 57 parts branched.

EXAMPLE 4 I The procedure of Example 1 was followed and 27.0 g.propylene was added to 0.50 g. palladium dichloridebis(triphenylphosphine) 0.50 g. anhydrous stannous chloride, 0.10 g.hydrogen chloride and 22.7 g. methanol in 43.1 g. p-xylene. Thetemperature was C. and carbon monoxide replenished to maintain apressure of approximately 900 psig for 6 hours. The product consisted of31 g. of methyl butyrate esters in a straightzbranched ester ratio of72:28 parts.

EXAMPLE 5 Following the procedure of Example 1, 20 g. propylene wasadded to 0.50 g. palladium dichloride bis(triphenylphosphine), 0.1 g.hydrogen chloride, 1.82 g. triphenylphosphine, 20.6 g. methanol in 43.1g. p-xylene. Carbon monoxide was added to 1,000 psig at 80C. for 6hours. The yield of methyl butyrate esters was approximately 1 percentand selectivity was 75 parts straight to 25 parts branched ester.

EXAMPLE 6 Following the procedure of Example 1, the autoclave wascharged with 20 g. propylene, 20.6 g. methanol, 0.3 g. hydrogenchloride, 1.82 g. triphenylphosphine, 0.5 g. palladium dichloridebis(triphenylphosphine), 0.25 g. stannic chloride pentahydrate and 43.1g. pxylene. At C. and 1,000 psig carbon monoxide pressure (total), 2grams of ester product were formed in 6 hours. The ratio ofstraight-chain to branched ester was 81 parts to 19 parts.

EXAMPLE 7 Following the procedure of Example 1, the charge consisted of20 g. propylene, 22.7 g. methanol, 0.50 palladium dichloridebis(triphenylphosphine), and 0.18 g. stannic chloride in 43.1 g.p-xylene. Carbon monoxide was added to maintain a pressure ofapproximately 900 psig. at 90C. for 5 hours. The product consisted of22.4 g. methyl butyrate esters, 75 parts straight-chain and 25 partsbranched.

EXAMPLE 8 Following the procedure of Example 1, the autoclave wascharged with 20 g. propylene, 27.4 g. methanol 0.50 g. palladiumdichloride bis(triphenylphosphine), 0.41 g. triphenyltin chloride, 2. g.hydrochloric acid and 43.1 g. p-xylene. Carbon monoxide was added for atotal pressure of 980 psig. at 95C. After 3 hours, 34.5

ester product were formed in a straight:branched ratio of 49:51 parts.

EXAMPLE 9 The procedure of Example 1 was followed and 26.9 g. l-butenewas added to 0.56 g. palladium dichloride bis(triphenylphosphine), 0.10g. hydrogen chloride and 12.8 g. methanol in 40.0 g. p-xylene. Thetemperature was 90C. and carbon monoxide replenished to main-' tain apressure of approximately 800 psig for 2 hours.

The product consisted of 38.8 g. of esters in a straightzbranched esterratio of 43:57 parts.

EXAMPLE 10 Following the procedure of Example 1, 12.1 g. l-butene wasadded to 0.52 g. palladium dichloride bis(triphenylphosphine), 0.57 g.anhydrous stannous chloride, 0.1 g. hydrogen chloride, 12.8 g. methanolin 40.0 g. p-xylene. Carbon monoxide was added to approximately 800psig. at 85C. for 4 hours. The yield of esters was approximately 85percent and selectivity was 71 parts straight to 29 parts branchedester.

EXAMPLE 11 Following the procedure of Example 1, the autoclave wascharged with 28 g. l-pentene, 12.8 g. methanol, 0.1 g. hydrogenchloride, 0.5 g. palladium dichloride bis(triphenylphosphine), and 40.0g. tetradecane. At 85C. and about 900 psig carbon monoxide pressure(total), 15.49 g. of ester product were formed in 4.5 hours. The ratioof straightchain to branched ester was 69 parts to 31 parts.

EXAMPLE 12 EXAMPLE 13 Following the procedure of Example 1, theautoclave was charged with 28 g. 2-pentene, 12.8 g. methanol, 0.55 g.palladium dichloride bis(triphenylphosphine), 0.1 g. hydrogen chlorideand 40 g. tetradecane. Carbon monoxide was added for a pressure of about900 psig. at C. After 6 hours, 10.2 g. ester product were formed in astraightzbranched ratio of 8:92 parts.

EXAMPLE 14 The procedure of Example 1 was followed and 28.0 g. 2-pentenewas added to 0.55 g. palladium dichloride bis(triphenylphosphine), 1.06g. anhydrous stannous chloride, 0.10 g. hydrogen chloride and 12.8 g.methanol in 40.0 g. tetradecane. The temperature was 85C. and carbonmonoxide replenished to maintain a pressure of approximately 900 psigfor 2.25 hours. The product consisted of 16.4 g. of esters in astraightbranched ester ratio of 30:70 parts.

EXAMPLE 15 Following the procedure of Example 1, 27.7 g. l-hexene wasadded to 0.50 g. palladium dichloride bis(triphenylphosphine), 0.1 g.hydrogen chloride, and 10.4 g. methanol. Carbon monoxide was added toabout 900 psig. at C. for 2 hours. The yield of esters was approximately72 percent and selectivity was 62 parts straight to 38 parts branchedester.

EXAMPLE 16 Following the procedure of Example 1, the autoclave wascharged with 34 g. l-hexene, 12.8 g. methanol, 0.1 g. hydrogen chloride,0.51 g. palladium dichloride bis(triphenyl-phosphine), and 0.51 g.anhydrous stannous chloride. At 90 C. and about 900 psig carbon monoxidepressure (total), 26.9 g. of ester product were formed in straight-chainhours. The ratio of straight-chain to branched ester was 86 parts to 14parts.

EXAMPLE 17 Following the'procedure of Example 1, the charge consisted of45 g. l-octene, 12.8 g. methanol, 0.52 g. palladium dichloridebis(triphenylphosphine) and 0.1 g. hydrogen chloride. Carbon monoxidewas added to maintain a pressure of approximately 900 psig at 80C. Theproduct consisted of 19.7 g. esters, 68 parts straight-chain and 32parts branched.

EXAMPLE 18 Following the procedure of Example 1, the autoclave wascharged with 90 g. l-octene, 32 g. methanol, 1.28 g. palladiumdichloride bis(triphenylphosphine), 1.24 g. anhydrous stannous chlorideand 0.25 g. hydrogen chloride. Carbon monoxide was added for a totalpressure of about 800 psig. at 80 C. After 3 hours, 94.2 g. esterproduct were formed in a straightzbranched ratio of 86: 14 parts.

EXAMPLE 19 The procedure of Example 1 was followed and 17.0 g.cis-2-hexene was added to. 0.50 g. palladium product consisted of 4.4 g.

dichloride bis(triphenylphosphine), 0.75 g. anhydrous stannous chloride,0.10 g. hydrogen chloride and 6.4 g. methanol in 40.0 g. tetradecane.The temperature was 95C. and carbon monoxide replenished to maintain apressure of approximately 900 psig for 0.5 hour. The of esters in astraightbranched ester ratio of 38:62 parts.

EXAMPLE 20 EXAMPLE The procedure of Example 1 was followed and 101.0 g.l-octadecene was added to 0.5 g. palladiumdichloride'bis(triphenylphosphine), 0.75 g. anhydrous stannous chloride,0.45 g. triphenylphosphine, 0.1 g. hydrogen chloride, and 12.8 g.methanol in 20.0 g. tctradecane. At 95C., carbon monoxide was added tomaintain a pressure of approximately 900 psig. After five hours, 53.3 g.of nonadecanoic acid esters were formed in a straightzbranched ratio of92:8 parts.

ple 3. shows that the use of a catalyst with a triphenylphosphine ligandand no tin cocatalyst or promoter gives a low 0.75:1 ratio of normalzisoproduct. Of the examples under about the same conditions and also usinga solvent (i.e., Examples 2, 4, 7 and 8) with the same catalyst and atin cocatalyst or promoter, the ratios range from 0.96:1 to 3:1. Theuse-of extra triphenylphosphine in the reaction mixture (i.e., Example5) increases the ratio, also, but at great expense in rate of reactionand lowered conversion. However, using the same amount of extratriphenylphosphine plus a tin cocatalyst or promoter significantlyincrease the ratio above even that value (e.g., Example 6 compared toExample 5). Examples 9 through 18 also show the effect of the presenceof a tin cocatalyst or promoter on the. carbonylation process involvinghigher unsaturated hydrocarbons. In each case, products with a higherratio of normalziso-ester or acid are provided when the tin cocatalystor promoter is present.

What is claimed is:

1. In a liquid phase process for the carbonylation of olefinicallyunsaturated hydrocarbon compounds to carbonyl-containing compounds byreacting the olefinically unsaturated hydrocarbon compound with carbonmonoxide and with a hydroxylic compound selected from the groupconsisting of alcohol, phenol and water in the presence of a palladiumsalt catalyst having the formula L,,,P X,, in which L is an organicphosphine, X is an acid function selected from the group consisting ofhalide, sulfate, phosphate, acetate,

TABLE.CARBONYLATION OF OLEFINS Selectivity, Mole ratio normal: Percentof co- ISO Example convercatalyst: weight number Olefin Coeatalystsion/hrs. 1 catalyst 4 ratio 1 Propylene Stannous chloride dihydrate46/3 2:1 1: 1 2- --do. ..do 87/3. 3 4.1 1. 9: None 89/3. 3 0. Anhydrousstannous chlorid 2 64/6 3. 7: 1 2. 6: Triphenylphosphine 2 l/6 10: 1 3riphenylphosphine/stannic chloride pentahydrate. 4/6 3 11:1 4. 3:Anhydrous stannic chloride 46/5 1:1 3. 'Iriphenyltin chloride 72/3 1.5:1 0. 96: None 83/2 0. 75: Anhydrous stannous chiorid 2 85/4 4:1 2. 45:

None 55/45 2.3- 0 Anhydrous stannous chloride 2 30/3 4:1 8. 4: one 20/60.09: Anhydrous stannous chloride. :1 0. 43: 1 None 2/2 1. 6: oAnhydrous stannous chlorid 8:1 6. 2: 17 l-octene None 2 49 1: 1 m .-doAnhydrous stannous chloride 2. 7:1 6- 2: 9 H (:iS-Z-hexene ..do 16/0. 65. 5: 1 0. 61 20 v 1-hexene/l-tetradecene ..do 20/1. 5 5. 5:1 a: 21l-octadecene ..do 43/5 5. 1 '11. 5:

Notes: 1 Temperature= C. 1 Tem erature=8085 C. 3 1 mo e tin salt/10moles triphenylphosphine/l mole catalyst. 4 Catalyst=pallad1umdichloride bis(triphenylphosphine).

5 This preparation was allowed to proceed overnight. The mixture ofolefins was in a mole ratio of 1:1. 1 For 01. 5 F01 0115.

As will be noted from the data of the examples as set forth herein, thecarbonylation process of the present invention provides products with ahigher ratio of normal: iso ester or acid when an appropriate hydroxyliccompound such as an alcohol or water is reacted with an olefin andcarbon monoxide. Of the examples emnitrate, propionate and borate, m isan integer of from 1 to 4, inclusive, and y is an integer of l or 2, thesum of m+y being an integer of from 2 to 6, inclusive, the improvementwhich comprises using a tin cocatalyst or promoter selected from thegroup consisting of inortin chlorides and triphenyltin chloride in anploying an appropriate solvent (ie p -xylene), Exam: amount sufiicientto increase the ratio of straight chain to branched chain compounds inthe reaction product.

2. A process as defined in claim 1, wherein the temperature is fromabout C. to about 200C.

3. A process as defined in claim 1, wherein the hydroxylic compound isan alcohol and the temperature is from about 60C. to about 100C.

4. A process as defined in claim 1, wherein the olefinically unsaturatedhydrocarbon has from two to 30 carbon atoms.

5. A process as defined in claim 1, wherein the olefinically unsaturatedhydrocarbon reactant is a physical mixture of two or more olefinicallyunsaturated hydrocarbons.

6. A process as defined in claim 4, wherein the hydroxylic compound isan alcohol and the temperature is from about 60C. to about 100C.

7. A process as defined in claim 4, wherein the acid function is ahalide.

8. A process as defined in claim 7, wherein the acid function ischloride.

9. A process as defined in claim 4, wherein the tin cocatalyst orpromoter is stannous chloride dihydrate.

10. A process as defined in claim 4, wherein the tin cocatalyst orpromoter is anhydrous stannous chloride.

11. A process as defined in claim 4, wherein the tin cocatalyst orpromoter is stannic chloride pentahydrate.

12. A process as defined in claim 4, wherein the tin cocatalyst orpromoter is stannic chloride.

13. A process as defined in claim 4, wherein the tin cocatalyst orpromoter is triphenyltin chloride.

gig UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTIUN Patent No. 3707 6 I Dated October 2 L 1972 I Inventor(s) Stephen A. Butter It iscertified that error appears in the above-identified patent and thatsaid Letters Patent are hereby corrected as shown below: I

F- Col. 5, Line 19, "34.5 should read YALE- g. 1

Col. 6, Line MO, "straight-chain hours" should read 1.75 hours Col. 7',Line 22, "Example" should be centered as Example 21 Col. 7 a 8 (TABLE)col L, line 19, "15/0. 6" should read l5/O.5

Signed and sealed this 6th day of March 1973 (SEAL) Attesc':

EDWARD M.,FLETCHER,JR. ROBERT GOTTSCHALK Attesting Officer Commissionerof Patents Notice of Adverse Decision in Interference In InterferenceNo. 98,553, involving Patent No. 3,700,706, S. A. Butter, SELECTIVECARBONYLATION OF OLEFINICALLY UN SATU- patentee was rendered Feb. 11,1976, as to claims 1, 2, 3, 4:, 6, 7, 8 and 9.

[Ofiez'az Gazette September 20, 1977.]

2. A process as defined in claim 1, wherein the temperature is fromabout 20*C. to about 200*C.
 3. A process as defined in claim 1, whereinthe hydroxylic compound is an alcohol and the temperature is from about60*C. to about 100*C.
 4. A process as defined in claim 1, wherein theolefinically unsaturated hydrocarbon has from two to 30 carbon atoms. 5.A process as defined in claim 1, wherein the olefinically unsaturatedhydrocarbon reactant is a physical mixture of two or more olefinicallyunsaturated hydrocarbons.
 6. A process as defined in claim 4, whereinthe hydroxylic compound is an alcohol and the temperature is from about60*C. to about 100*C.
 7. A process as defined in claim 4, wherein theacid function is a halide.
 8. A process as defined in claim 7, whereinthe acid function is chloride.
 9. A process as defined in claim 4,wherein the tin cocatalyst or promoter is stannous chloride dihydrate.10. A process as defined in claim 4, wherein the tin cocatalyst orpromoter is anhydrous stannous chloride.
 11. A process as defined inclaim 4, wherein the tin cocatalyst or promoter is stannic chloridepentahydrate.
 12. A process as defined in claim 4, wherein the tincocatalyst or promoter is stannic chloride.
 13. A process as defined inclaim 4, wherein the tin cocatalyst or promoter is triphenyltinchloride.